Manufacture of coating compositions



, Ser. No. 273,159, filed Apr.

Patented Aug. 18, 1942 OFFICE I MANUFACTURE or comma comosrrrons LaszloAuer, Bloomfield, N. J.

No Drawing. Application November 20, 1939, Serial No. 305,409. InHungary May 19, 1926 p 18 Claims.

This invention relates to the manufacture of coating compositions and itcomprises varnishes, lacquers and other coating compositions containingmodified organic isocolloid materials, such as modified fatty oils,etc., the physical and other properties of which have been modified withthe aid of and by means of a minor amount of a polar compound,and'particularly nitrocellulose compositions containing such modifiedorganic isocolloids which may advantageously be a modifled fatty oil,and itv also comprises methods of making such coating compositionswherein the organic isocolloid material, such as a fatty oil,

, etc., is modified with a minor amount of a polar compound, usually byheating those materials to a suitable temperature sufiicient to effectthe desired modification thereof, and the modified fatty oil or otherorganic isocolloid material is dissolved in organic solvent or mixtureof such solvents and is sometimes also blended with other varnish andlacquer, ingredients as desired to obtain compositions useful as and incoating compositions, such as paints, enamels, varnishes, lacquers andother liquid and plastic compositions, all as more fully hereinafter setforth and as claimed.

In my prior applications which are more fully identified post, I havedescribed processes of modifying thephysical and other properties oforganic isocolloids, such as fatty oils, resins, etc., with the aid ofpolar compounds. As stated in my prior applications, the modifiedorganic isocolloid materials obtained from fatty oils, resins,

(Cl. 106-171) I Ser. No. 273,160, filed Apr. 26,- 1928; now Patent Ser.No. 359,424, filed Apr. 30, 1929; now Patent Ser. No. 359,425, filedApr. 30, 1929; now Patent Ser. No. 359,426, filed Apr. 30, 1929; nowPatent Ser. No. 359,427, filed Apr. 30, 1929; now Patent Ser. No.446,170, filed Apr. 21, 1930; now Patent Ser. No. 446,171, filed Ap 21,1930; now Patent Ser. No. 446,172, filed Apr. 21, 1930; now Patent Ser.No. 446,174, filed Apr. 21, 1930; now Patent Ser. No. 466,587, filedJuly d, 1930; now Patent 2,106,708

. Ser. No. 188,014,-fi1ed Jan. 31, 1933 As disclosed in the aboveapplications, I have found that by modifying organic isocolloids with invarious commercial arts and for many industrial purposes; those obtainedfrom fatty oils and etc., by the processes there described, are usefuland advantageous in making varnishes and lacquers and other liquid andplastic compositions.

The present invention, as stated ante, is directed to the manufacture ofcoating compositions containing such modified organic isocolloidmaterials, particularly modified fatty oils. 'And it is a continuationin part of my prior applications; the various organic isocolloids andpolar compounds or modifying agents and the several procedures disclosedin such prior applications being useful in the present invention and inthe commercial practice thereof.

This application is a continuation in part of my prior applicationSerial No. 446.174, fi ed p l resins being generally useful in makingvarnishes and lacquers.

In the processes described in the said prior applications, the modifyingagents are employed in minor amounts by weight on the fatty'oil or otherorganic isocolloid material. The modifying agents are inorganic andorganic compounds which are electrolytes or polar compounds capable ofinfluencing the modification of the Organic isocolloid substances. Withthe aid of and by means of, such polar compounds, I have modified theviscosity, melting point, solubility and other physical properties oforganic isocolloids as described and disclosed in said priorapplications.

21, 1930. That application,in turn, is a -con-' tinuation in part of myearlier application Serial No. 143,786, filed October 23, 1926, and ofthe various divisions and continuations of that parent application,particularly the continuation thereof filed April 30, 1929, Serial No.359,425.

The said parent application and the continuations thereof are asfollows:

' Ser. No. 143,786, filed Oct. 23, 1926; now Patent 26, 1928; now PatentIn those applications many illustrative examples of the practice of mygeneric invention are I disclosed. As stated in 'my prior applications,

such as Ser. Nos. 446,170 and 446,174, illustrative organic isocolloids,or starting materials suitable for modification by my processes, arefatty oils, waxes (animal, vegetable, etc), natural resins such asrosins, etc., synthetic resins containing natural resins, productscontaining the acids of fatty oils and resins and their derivatives,such as esters of. fatty and resin acids, mineral oils, particularlymineral oils containing naphthenic acids, certain mineral oil products,tar, asphalts, goudrons (petroleum distillation residue), pitch,

rubber and rubber-like hydrocarbons, etc. also chemically pureisocolloids bodies such as styrene, etc. All of the abovemat'erials andother like organic isocolloids may be modified with the aid used in theabove example 'is an inorganic salt; temperatures between 250 to 350 C.being sometimes used in such cases.

Such methods are disclosed in my copending application Ser. No. 143,786,mentioned ante as the parent application. In that application, Idescribe processes for the modification of the physical properties ofnatural and artificial organic isocolloids, such as fatty oils, resins,etc., with the aid of and by means of electrolytes under which term areincluded organic and inorganic acids, salts of such acids and metallicderivatives of organic compounds (organic metal compounds), separatelyor mixed. In most of the methods there described, the organic isocolloid(starting material) such as a fatty oil, is heated with a minor amountof the'electrolyte or polar compound, at reduced, ordinary or increasedpressure; with or without simultaneous or subsequent treatment withsulfur or sulfur compounds such as sulfur chloride, or with gases.Again, the organic isocolloid and the electrolyte may be mixed cold,that is, the modifying agent incorporated at room temperature in theorganic iscolloid to be modified. This is advantageous when themodifying agent or polar compound is directly soluble at roomtemperature in the organic iscolloid being modified thereby. Also themixing and/or heating may be done in the presence of organic bodies,such as phenols, naphthols, naphthalin, chloroform, acetone, alcohols,formic acid, acetic acid, their homologues and derivatives, etc., whichmodify certain physical properties, such as'adhesion, elasticity, etc.of the products obtained; some of these organic bodies being organicsolvents. As

stated therein, the mixtures are usually heated to temperaturesconsiderably above room temperature and below the boiling point of theorganic isocolloid being so modified. For instance, the electrolyte andthe organic isocolloid may be melted together, that is, fused together.Likewise, the specific, illustrative examples given in Ser. No. 143,786are advantageous for fatty oils, such as linseed oil, rapeseed oil,etc.; even solid oil'products, as well as viscous oil products, beingobtained as desired. One such example is as follows:

Example 1.-'-To 100 grams of linseed oil are added 5 grams of potassiumthiocyanate. The mixture is heated in a vacuum for 2 hours at atemperature between 300 and 350 C. At the end of this time, the vacuumis broken and the modified oil product is poured into molds and allowedto cool. I

- In the above example, if desired, '5 grams of cobalt linoleate may beaddedto the oil in addition to the potassium thiocyanate. The cobaltlinoleate is' drier or siccative as is well known in the varnishindustry. It serves to further modify the oil product so obtained.

Also rapeseed oil or other fatty 911 may be in lieu of linseed oil toobtain other modified fatty oil products.

Likewise, other metal salts may be substituted for the potassiumthiocyanate in the above example to produce still other modified fattyoil products. For instance, ammonium iodide and in the processesdescribed therein.'

may be used in place of salts; both inorganic and organic acids andtheir salts being disclosed in that application as useful modifyingagents That is, the polar compound employed as the modifying agent maybe an acidic compound, either an or ganic or inorganic compound.

In other words, as stated in Ser. No. 143,786, I may use as themodifying agent, salts, acids and organic metal compounds, eitherseparately or mixed. In the present invention I may do likewise and suchcompounds containing the following cations' or anions or both, areadvantageous:

as cations;

Ammonium Sodium Potassium Lithium Strontium Calcium Barium MagnesiumIron (ferric and ferrous) Cobalt Aluminum Lead Antimony Manganese Tin(stannic and stannous) Cadmium Bismuth Zinc Organic ammonium ions, etc.

as anions;

Thiocyanic (acid) Maleic (acid) Salicylic acid) Ehthalic (acid)Sulphanilic (acid) Naphthenic (acid) Thus; salts of inorganic and oforganic acids may be used; both aromatic and aliphatic organic acids.Some are salts of monobasic acids and others of, polybasic acids,particularly dibasic acids. Both neutral and acid salts may be used.

As described in my copending application Ser.

No. 359,425, filed April 30, 1929, as a continuation 2,288,038 in partof Ser. No.143,786, further investigations enabled me to indicate somespecial features of particular series of examples of the main inventionand to add valuable groups of modifying Tung oil Linseed oil Castor oilFish oil (train oils) Poppy-Seed oil Sunflower oil Rapeseed oil Walnutoil Pipe oil Corn oil Olive oil the ease of transformation under equalconditions decreases in the order given; the first mentioned oil beingmost rapidly and readily modified. It should, however be mentioned, thatmodified oil products can also be readily obtained from even the lastmentioned oils with suitable modifying agents.

As there stated, I have found that those modifying agents are mosteffective which according to Frumkins method (see e. g. Z. physikalischeChemie, 1924, 109, 34-49 and later papers) impart a negative surfacecharge to a liquid in which they are dispersed.

Ifurther, in Ser. No. 359,425, I disclose that in addition to salts andacids, I may also use organic polar compounds to modify fatty oils andother organic isocolloids. A large number of typical organic polarcompounds are listed there as illustrative of those which areadvantageous in my processes. Many specific embodiments of my genericinvention are shown in that application.

As shown in Ser. No. 359,425 many different types of organic polarcompounds may beemployed in my processes. However, the organic polarcompoundsas a class are advantageous as there stated. As a class theyare more readily soluble in the organic isocolloids generally and aresoluble in many types of organic solvents, particularly the volatileorganic solvents ordinarily used in making lacquers and varnishes andother coating compositions. Thus the organic polar compounds can be moreeasily incorporated in the organic isocolloids as the modifying agentand this is advantageous. For instance, in using organic polarcompounds, the modification of the organic isocolloid may be effected atlower temperatures than given in the example ante;

in many cases, at temperatures as low as 100 C. In some cases, even roomtemperature may be used, the materials being mixed cold as stated inSer. No. 143,786. However, as stated in both Ser. Nos. 143,786 and359,425, it is desirable and advantageous to heat the mixture to asuitable temperature until the desired modified product is obtained; thematerials being melted or fused together. Generally temperatures between100 and 300 C. give satisfactory products for most purposes. Of course,the temperature and time of heating depend upon the materials employedand the type of product desired.

This is particularly so with the organic polar compounds disclosed inSer. No. 359,425. As there disclosed, the organic polar compounds mayadvantageously be salts of organic acids, salts of organic bases,organic acids, organic bases,

- metallic derivatives of organic compounds and other organic, polarcompounds which contain a group or groups imparting polarity to theorganic -'compounds; those containing a plurality of such groups beingadvantageous.

An advantageousclass of organic polar compounds, set forth in Ser. No.359,425 (and in the continuations thereof, such as Ser. Nos. 446,170,446,172, 446,174, etc. filed on April 21, 1930, and Ser. No. 188,014filed Jan. 31, 1938) are the organic polar compounds comprising with themolecule an acidic inorganic residue and an organic residue (by anacidic inorganic residue I mean such an inorganic residue as can beconverted by the addition of one or more hydrogens into an inorganicacid, including carbonic acid as inorganic). This class of organic polarcompoundsv is a broad one and such compounds may be represented by thefollowing generic formula R-Xn, wherein R represents the organic residueand X represents the inorganic acidic residue; the n being 1 to 5. Theacidic inorganic groups may be nitro, halogen, sulphur-containingradicles, carboxyl, etc. and one or more such groups may be present inthe molecule and attached to the organic residue.

One advantageous class of theselpolar compounds are the organic halogencompounds, both aromatic and aliphatic, containing chlorine, io- Y dine,bromine, etc. and the following compounds are typical and illustrativeof this class;

' o-Dichlorobenzene p-Dichlorobenzene Trichlorobenzene v Naphthalenetetrachloride Naphthalene trichloride Naphthalene hexachlorideNaphthalene monochloride v Nitro-chlorobenzenes, ortho, meta and para 7N itro-dichlorob enzenes Chloro dinitrobenzenes MonochlorobenzeneChlorinated diphenyl Pinene hydrochloride 4'-chloro-o-anisidinep-Nitro-chloro-benzene Triphenyl-chloro-methane Benzyl chloride Benzoylchloride Acetyl chloride Acetyl bromide Phthaloyl chlorideTriohloroacetic acid Monochloroacetic acid Chloral hydrate Iodoform Thehalogen compounds listed ante and other halogenated aryl and aliphaticcompounds, including acyl chlorides, chloro-acids, hydrochloride salts,etc. may be used in the practice of the present invention. And from thelist given ante and as shown in my prior applications, such halogenatedcompounds may also contain other subtogether with 5 parts advantageousin the practice of the present invention. And nitro organic compoundsare another advantageous class of organic polar compounds. The followlngnltro compounds are typical and illustrative of this class:

Ethyl thioether of nitro-arninobenzene 2 4-dinitrobenzeneNitro-aminobenzene These illustrate the various general types of nitrocompounds which may be used in addition to the nitro compounds shown inthe other classification of these polar compounds.

Another advantageous class of modifying agents or polar compounds arethe aromatic sulphonic acids, together with their salts, esters andhalides. Of these sulphonyl chlorides are particularly useful here. Theyare advantageous for modifying fatty oils, particularly linseed oil,castor oil, etc. and for resins.

These polar compounds may be represented by the following genericformula R--SO1i -Y, wherein R represents an aryl nucleus, Y representshydrogen, chlorine or an alkyl group or a metal and n is to 4. Typicalexamples of such compounds are the following compounds:

Benzene sulphonic acid p-Toluene sulphonic acid 2:5 dichlorobenzenesulphonic acid m-Xylidine sulphonic acid p-Toluidine-m-sulphonic acidNaphthalene 2:6 sulphonic acid Beta-naphthol 1:5 sulphonic acidBeta-naphthol 3:6:8 sulphonic acid Beta-naphthylamine 3:6:8 trisulphonicacid 2:1 naphthylamine sulphonic acid 2:6 naphthylamine sulphonic acid2-phenylamine-8-naphthol-fi sulphonic acid Methyl-p-toluene sulphonatethe f Ethyl'chlorosulphonate i" Benzene sulphonyl chloride p-Toluenesulphonyl chloride Naphthalene-l-sulphonyl chloride Dimethyl sulphateDiaminodihydroxy anthraquinone disulphonic acid.

Metal salts of such sulphonic acids, such as the sodium salts, are alsouseful here in the present methods. Specific embodiments of this phaseof my invention are given in my prior applications Ser. Nos. 359,425 and446,174. One such example is as follows:

Example 2.--150 parts in vacuum to 280-310" C. for 5 hours with 7.5parts of 2:5 dichlorobenzene sulphonic acid. A soft solid product isobtained, suitable for use an a'base for the manufacture of varnishes.

other example is as follows:

Example 3.-100 parts of castor oil are heated of 2:5 dichlorobenzenesulphonic acid in vacuo for 5 hours at 260 C. The

the sulphonic acids and the present invention.

of linseed oil are heated product is a thick viscous oil, soluble inbutyl acetate, in acetone and in benzene. It is useful in makinglacquers, particularly nitrocellulose lacquers and coating compositions,such as leather cloth compositions.

Another advantageous class of polar compounds set forth in my Ser.359,425 and useful in the present invention, are the organic esters ofinorganic acids, both aryl and alkyl esters. The following areillustrative of this class:

'I-riphenyl phosphate Tricresyl phosphate and other alkyl-phenylphosphates Nitrocresyl carbonate Ethyl chlorosulphonate Dimethylsulphate In addition to these, other alkyl and aryl esters ofinorganicacids such as borates, phosphates, phosphites, sulphides, sulphates,thiocyanates, etc. may be used; for instance, propyl, butyl, amyl andiso-alkyl esters. Likewise, esters of various aliphatic alcohols andphenolswith organic acids may be used as shown post.

Still another class of modifying agents or polar compounds, set forth inSer. No. 359,425 and useful in this invention, are the inorganic saltsof organic bases, of which the following compounds are illustrative:

Diphenylamine hydrochloride Diphenylamine hydrobromide m-Nitroanilinehydrochloride Trichloroaniline hydrochloride Diphenyl amine sulphateDiaminodiphenyl sulphate Aniline sulphate Amino-azo-benzene sulphate 4:4diamine-diphenyl sulphide Aniline hydrochloride amine trichloroacetateand methyl p-toluene Other wholly organic salts may be used. Forinstance, the alkyl and aryl esters of the various organic a idsmentioned ante, such as-tartrates, oxalates, acetates, formates,thiocyanates, salicylates, etc may be used in the These are illustrativeof the esters of monoand di-basic acids which may be employed.

Likewise, alkyl and phenyl esters of other allphatic and aromaticcarboxylic acids, both monoand di-basic acids, such as phthalates,benzoates, acetates, abietates, oleates, laurates, palmitates,ricinoleates, etc. may be used. Both the monoand di-esters of di-basicacids are useful here. Likewise mixed alkyl and aryl esters andalkylated phenyl esters can be employed in some cases. Typical examplesare as follows:

Di-butyl .phthalate' Mono-btuyl phthalate Di-ethyl phthalate Ethyl butylphthalate Di-phenyl phthalate sulphonate.

Ethyl-phenyl tartrate Methyl abietate v Ethyl abietate I Di-ethylsuccinate Phenyl thiocyanate Ethyl malonate Diethylammoniumdiethyldithiocarbamate Ethyl salicylate Methyl salicylate Ethyl ether ofethyl salicylate Butyl ether of ethyl ricinoleate That is, etheresterand acid esters may be also employed here. Further, thioethers such asdiaminodiphenyl sulphide, may also be used; they nitrobenzene. That is,the phenyl group of such sulphides or thiothers may be furthersubstituted with. groups such as amino, nitro, etc.; these groupsincreasing the polarity of the molecule.

Many of the polar compounds illustrated ante in the variousclassifications also contain amine or amino groups. In the presentinvention amine compounds as a class are useful. My prior applicationSer. No. 446,170, Patent No. 2,234,949 is primarily directed tomodifying fatty oils and other organic" isocolloids with amine compoundsas the polar compound or modifying agent. As

there disclosed, amines having a relatively high molecular weight areadvantageous.

In the present invention, as in the methods of my prior Ser. No.446,170, compounds containing primary, secondary or tertiary aminegroups and containing one or more of such amine groups may be used asthe modifying agent; those containing two such groups beingadvantageous. Any and all of the specific amine compounds disclosed inSer. No. 446,170 and my other prior applications may be used in thepractice of the present invention.

One of the advantages of the amines as modifying agents is that they arerelatively easier to dissolve or disperse in fatty oils and otherorganic isocolloids to modify them. H

The amines may be used by themselves or in conjunction with othermodifying agents, etc, in modifying organic isocolloid materialsaccording to the present invention. For instance, the

' amines may be used in conjunction with polar compounds comprisingwithin the molecule an acidic inorganic residue and an organic residue,such as given ante. Sometimes they may be disclosed in my prior Ser. No;446,174 wherein the use of nitrophenols is specifically claimed.However, in most embodiments of the present invention, such organicbases are used in conjunction with other modifying agents, they beingemployed to give an additional modification in the properties oftheproducts obtained, as pointed out in my applications Ser. Nos.143,786, 359,425,

. and 446,174. The organic bases may be used used with certain auxilarymaterials, as shown inSer. No. 446,170 and other of my priorapplications.- Again, it is sometimes advantageous to use, as themodifying agent, an organic polar compound containing both an aminegroup and an acidic residue, such as the aromatic amino sulphonic acidsand other compounds of that type shown ante. That is, the various aminesand procedures disclosed in Ser. No. 446,170 may be used in the practiceof the present invention.

In addition to the amines, I may also use other organic bases asmodifying agents in the present processes. Many such organic bases aredisclosed in my prior applications; for instance,

naphthols, phenols, etc. as described in my prior applications Ser. Nos.143,786, 359,425, 446,174 and 188,014. In Ser. No. 188,014 many typicaland illustrative organic bases are listed and all of them are usefulhere. As shown in those applications, a wide range of organic bases maybe used, according to the type of modified product desired.

The direct use of organic bases, such as arylhere in conjunction withmetal salts, acids, acid chlorides (acyl chlorides) etc. employing theproportions and procedures shown in said prior applications. As statedante, such polar compounds are advantageous modifying agents when usedalone.

In fact, the acids are an important class of polar compounds and may beused alone as the modifying agent in the practice of the presentinvention. Certain of the advantageous acids,

particularly the organic acids, have been described ante. In addition tothose disclosed in my Ser. Nos. 143,786 and 359,425,.any and all ofthose listed in my Ser. No. 188,014 may be used in the presentinvention; the inorganic as well as the organic acids. In connectionwith the salts and esters, I mention many acids and these are suitablefor use here in the form of the free acid as well as in the form ofmetalsalts and esters. As mentioned ante, acid salts and acid esters maybe used and these soto speak are partly neutralized acids; that is, theyare of acid character. Also the anhydrides and acid chlorides of theseacids are useful here as the modifying agent. As shown ante, the metalsalts of these acids may be used as the polar compound, here.

Also in Ser. No. 359,425 and the other continuations of Ser. No.143,786, notably my Ser. No. 446,174, I have given many specificexamples of metal salts, both neutral and acid salts, which areadvantageous in the practice of the present invention, particularly formodifying fatty oils and natural resins. are as follows:

Ammonium iodide Cadmium iodide Zinc bromide Barium thiocyanate Potassiumthiocyanate Ammonium chloride Magnesium chloride Magnesium sulphateSodium sulphate Sodium hydrogen sulphate Di-sodium hydrogen phosphateSodum bisulphite Sodium sulphite Lithium sulphite Lithium carbonate Zinccarbonate Sodium sulphide Barium sulphide Lead chromate Potassiumdichromate Cadmium sulphide Sodium bicarbonate 'Tin carbonate Tinsulphite Tin sulphide Tin chloride (stannous Antimony sulphide andstannic) Zinc sulphide Barium sulphide hydroxy compounds, as themodifying agent, is Barium carbonate Some of these my processes Calciumsulphite Strontium .sulphite Magnesium sulphite Barium sulphite Leadsulphite Cadmium sulphite Mercuric sulphate Metal salts of inorganicacids Metal salts of organic acids Organic salts of organic acidsOrganic salts of inorganic acids Organic bases Organic acids Inorganicacids Organic halogen compounds Organic nitro compounds Organicsulphonio compounds Metallo-organic compounds Most of these modifyingagents are organic polar compounds, as is evident from theclassification given ante.

The amount of modifying agent, to wit, the polar compounds such as shownante, used in is a minor amount by weight on the organic isocolloid; anamount not exceeding 30 percent. Generally from 1 to 30 percent of thepolar compound is used. However, in some cases less than 1 percent givesdesirable improvements in the oil; sometimes as little as 0.01 percentbeing used. An advantageous range is from 0.01- to 10 percent of polarcompound on the fatty oil. Generally I find that the amount ofmodification of the final products increases with the amount of polarcompound used,,when the other conditions are the same.

The modifying agents should be added to the starting material in dryform (without the presence of water) and in relatively small quantities.dispersion of the modifying agent, the operation of dissolving ordispersing the latter should be carried out under pplication of heat.The temperature necessary depends upon the nature of the substance undertreatment and also of the modifying agent used. Generally temperaturesfrom 100 to 300 C. give satisfactory results.

The heat treatment promotes the complete (molecular or colloidal)dissolution of the modifying agent in the substance to be treated. In

some cases it may be advisable and advantageous to continue the heatingafter the dissolution -or dispersion of the modifying agent issubstantially complete. This is advantageous .in modifying fatty oils attemperatures of 250 to 300 C. with these polar compounds, for bycontinuing the heating several hours the oil is also heat-bodied and Iobtain modified, heatbodied fatty oil products particularly useful inmaking varnishes.

I have further found that the results of these processes vary with thepressure employedand with the nature and/or with the physical condition(pressure) of the gas (air or other gas) present in the reactionchamber. Thus I have In order to ensure complete dissolution or foundthat certain given starting material which is initially liquidwillbecome viscous only as theresult of the electrolyte treatment, if thelatter is effected under atmospheric pressure (e. g. in an open vessel),but solid if the gas is rarified by the employment of a partial vacuum.In other cases, the converse applies. When plus pressure was used (c. g.caused by the tension of the starting material at higher temperatures)the results differ again from both of those of the treatments underatmospheric pressure and vacuum. Also, as to the nature of the gaspresent, air gives for instance a different result from another gas ormixture of gases. The pressure conditions may be alternated during thegas treatment, which, of course, may be carried out together with thedissolution or dispersion of the modifying agent in the substance to betreated or as an after treatment.

It may be stated with reference to the action of gases that generallyspeaking rariflcation of the gases present in the reaction chamber byreduction .of pressure tends to intensify their action in the processboth in the case of solidification of the starting material and also inthe case of liquefaction thereof.

The gas treatment maybe carried out by blowing the gas through themixture or simply by passing it over the mass contained in the vessel.The gas may be hydrogen, nitrogen, carbon dioxide, hydrogen sulphide,sulphur dioxide, etc. and a current of such gases passed through the 011during the heating. In this way the bodying is facilitated as describedin my prior applications. The gas may also be produced in situ in themixture by using substances which under the conditions employed developthese gases, if desired. For instance. by using peroxides, carbonates,sulphides, sulphites and the like, the corresponding gases; may bedeveloped in situ during the heating.

My processes, as described ante and in my prior applications, may bemade to effect a solidification or a liquefaction of the initialmaterial. Thus, for instance, thickened products and even solidsubstances may be-obtained fromv thin oils. Similarly I have found thatresins either soft or liquid or of any intermediate stage of viscositymay be obtained from solid resins. The results, namely, solidificationon the one hand, or liquefaction on the other, depends in any given caseupon the conditions used, c. g. upon the time and temperature ofheating, the gas treatment, the quantity of dissolved modifying agent,etc. Generally speaking the products obtained were, from liquids, solidsor semisolid thermoplastic masses, and from solids, pasty or thinliquids;

If desired the modifying agent may be produced in situ within theorganic isocolloid under treatment by interaction within the substance,of compounds capable of reacting under the conditions of the process toproduce the modifying agent desired.

The dissolution or dispersion of the modifying agents in the startingmaterial may be favorably influenced by the addition of certainauxiliary agents" or sensitizers." These fall into two groups, namely,the purely inorganic agents such as silica gel, fullers earth and otherclays and the purely organic agents such as formaldehyde, phenol,thiocarbanilide, hexamethylenetetramine, 2:3 hydroxynaphthoic acid,alphanaphthol, quinoline. pyrogallol, benzene, glycerol and phthalimide.The specific examples of auxiliary agents here mentioned are to be takenas typical of the'substances which have been successfully used for thispurpose and not as comprising ,all the effective substances. It shouldbe mentioned that quite a number of the modifying agents comprisingwithin the molecule an acidic inorganic residue and an organic residueare also useful as auxiliary agents (sensitisers) when used inconjunction with other modifying agents. Thus, e. g. the dissolution ofof sodium bisulphite in linseed oil is facilitated and the color of theproduct is made lighter by the addition of say 2% of an auxiliary agentsuch as amino-azobenzene sulphate, aniline sulphate, nitrocresylcarbonate, dimethyl sulphate, trichloracetic acid, benzene sulphonicacid, iodoform; naphthalene tetrachloride, pinine hydrochloride,m-xylidine-sulphonic acid, betanaphthylamine-B:8-disulphonic acid,beta-naph thylamine 6 sulphonic acid, acetyl chloride,p-nitro-acetanilide, chloral hydrate, triphenyl phosphate,naphthalene-l-sulphochloride, diphenylamine hydrobromide, aminosalicylicacid, 2:6 naphthalene disulphonic acid, o-chlorobenzene.

The advantage of a rapid dissolution of the modifying agent are greatestin those cases where a clear, pale or colorless product is desired,especially for example in the varnish industry.

For the modification of the physical properties of the initialmaterials, solutions or colloidal solution of one or more electrolytesin an organic solvent may be used, as stated in my prior applications..-

Inall cases the treatment may be advantageously influenced by exposingthe materials un-' dergoing treatment to oscillating energy (X-rays,ultraviolet rays, infra-red rays, etc.) or by including the vessel in anelectric circuit.

Filling materials, pigments and the like may be added at any stage ofthe process.

All of the description given ante as to my processes and the materialsused therein is set forth in my prior applications wherein such methodsare fully illustrated with many specific examples.

In the present invention, I employ similar polar compounds andprocedures for modifying the same types of organic isocolloid materials,particularly fatty oils, to obtain modified isocolloid products for myimproved coating compositions to which the present application isdirected. That is, I may use any of the modified products disclosed inmy prior applications in making the lacquers, varnishes and othercoating compositions of the present invention, they being dissolved insuitable organic solvents and blended with other materials as shownpost.

As stated in my Ser. No. 446,174, I have found that the solubility inorganic solvents of my fatty oil products and other modified organicisocolloids, obtained by the processes set forth ante and described indetail in my prior applications, vary quite markedly and in part dependupon the particular polar compound employed. As there stated, I havefound that when my modified products are made with the aid of a polarcompound which itself is insoluble in certain organic solvents, themodified product so obtained is also insoluble or difiicultly soluble inthose particular solvents. On the other hand, as also stated in thatapplication, I have found that if the polar compound'employed is itselfsoluble in certain organic solvents, the modified products made with itare likewise soluble in the same solvents. For instance, ammonium iodideor other polar compounds soluble in acetone produce'modifled castor oilproducts which are also readily soluble in acetone, as disclosed in Ser.No. 446,174. Such modified products, being soluble in acetone, can beincorporated with solutions of nitrocellulose to obtain improvednitrocellulose compositions as there disclosed.

. Thus in preparing my coating compositions, one method of the presentinvention is to heat the fatty oil with a polar compound which itself issoluble in the organic solvent or solvents to be used in suchcomposition. Then the modified fatty oil so produced and containing suchpolar compound dissolved or dispersed therein, is dissolved in thematched solvent to obtain the desired solution. This simple method isadvantageous and can be used with any of my modified oil productsproduced with the aid of polar compounds which themselves are soluble invarnish and lacquer solvents, such as benzene, acetone and otherketones, butyl acetate and other ester solvents, methyl alcohol andother alcohols, etc. Also, my modified products, made with a polarcompound insoluble in such solvents, and which cannot be directly usedto prepare solutions in such solvents, can be made soluble in them byasubsequent treatment. In this subsequent treatment, the insolublemodified'oil product is fused with a minor amount of an organic compoundwhich is soluble in such solvents. The fused material so obtained cannow be dissolved in the said solvent or solvents and useful coatingcompositions obtained. This method can be also used to improve thesolubility in varnsh and'lacquer solvents, of unmodified organicisocolloids which are naturally diificultly soluble in these solvents.In either case, my polar compounds which are soluble in the saidsolvents may be used to so improve the solubility of these isocolloids,both the modified ones and the unmodified or natural ones. v

The two step method ante for making soluble modified oil products, byfirst using an insoluble polar compound as the primary modifying agentand then a soluble compound to convert the insoluble oil product'into asoluble one, may be simplified into a single step method by adding boththe insoluble and the soluble compounds to the oil in the beginning;both the primary modifying agent and the secondary or solubilizing agentbeing present during the initial heating.

All three of the above methods for making soluble oil products are givenin my Ser. No. 446,174 and other prior. applications set forth ante. Inmy Ser. Nos. 466,587 and 188,014, I also describe methods wherein afatty oil is first bodied without the addition of a polar compound andthen the bodied oils so obtained are heated with a polar compound tomodify them. Many of the polar compounds used in those processes aresoluble in varnish and lacquer solvents and the product obtained withthem are useful in making the present coating compositions.

In the fields of protective coatings and plastics it is very desirableto produce bodied fatty oils 'of predetermined solubility properties, orto obed in form of solutions.

my invention,

- belong to the class which or oil products certain agents thecharacteristic feature of which is their solubility in the medium inquestion. As mentioned hereinbefore the medium may be either a solventor a mixture of solvents and/or diluents or a solution of another filmforming agent or agents in solvents or solvent mixtures. I am thinkingprimarily of cellulose ester or cellulose ether solutions, such asagents may be ensured by the application of heat and the process can becarried out under atmospheric pressure, or under reduced pressure orunder plus pressure. The agents may be add- In the latter case thesolvents may be distilled off to obtain nonvolatile oil products. Ifmodified fatty oils are to be treated, the solution promoting agent maybe added either in the modifying process itself or after the oilproducts have undergone the modifying treatment. These methods areuseful in the alternative that the modifying agent itself is insolublein the solvent or solvent mixture or solution,'in which the fatty oilhas to be dissolved. Certain dissolution chosenfrom the class ofmodifying agents. If the modifying agent is soluble in the solvent orsolvent mixture or solution in question, it is possible to producemodified heat bodied fatty oil products with the desired solubilityproperties. In such an event the modifying agent itself is acting asdissolution promoting agent. It is possible of. course to use severalagents simultaneously, which each act as dissolution promoting promotingagents may be agent and of which some may act as modifying agent also.

The invention further consists of making protective coatings andplastics, containing such fatty oils of predetermined favorablesolubility properties on one hand and another film forming agent oragents on'the other hand, such as cellulose esters, cellulose ethers,chlorinated rubber, oleo-resinous varnishes, amongst others. .Thedissolution promoting agents, according to may be classified in thefollowing groups: (A) Such which are modifying agents themselves and (B)such which are not modifying the viscosity of fatty oils when heatedwith them at bodying temperatures. The group A, representing themodifying agents, being themselves well soluble in the media inquestion, may besubdivided into (1) inorganic and (2) organic agents.The inorganic dissolution promoting modifying agents require higherbodying tem peratures for their dispersion in the fatty oils. Usually250 C. is the lowest temperature limit and the decomposition temperatureof the oil is the upper limit. Practically 290 to 310 C. yieldsatisfactory products, in the most cases. The organic dissolutionpromoting modifying agents consists of an organic residue and aninorganic residue and which may develop on the action of heat in theoils acids,

cib

agents, which themselves aretemperatures below 200 C. Only very feworganic dissolution promoting agents require higher temperatures than200 C. for their dissolution or dispersion. If it is desirable that thedissolution promoting organic modifying agents should have a bodyingaction, then it is necessary to heat the oil to bodying temperatures,which is usually above 200 C. and in most of the cases even above 250C., with the temperature range of 270 to 320 C. being the mostly usedone. If the dissolution promoting modifying agent should only performthe promotion of the dissolution of the fatty oil product in question inthe different media above referred to, then the heating to bodyingtemperatures may be omitted and the process is concluded with thedispersion of the agent in the oil. The latter types of agents, topromote dissolution, may be used in addition to such inorganic agents oralso to such organic agents which are insoluble in the organic solvents,or-they may be used alone or in admixture with other dissolutionpromoting agents.

The group B representing the dissolution promoting agents whichthemselves have no appreciable modifying action on the viscosity offatty oils at bodying temperatures, are mostly organic compounds and maybe'used, like the organic dissolution promoting modifying agents, eitheralone or in admixture with modifying not soluble in the organic solventsin question. They may be heated with the oil to bodying temperatures orthey may be heated with the oil only until dispersion occurs. The oil tobe treated with group B may be a modified or a not modified fatty oil.

According to the present process vegetable or animal oils may betreated. .Synthetic resins of the fatty acid containing types of alkyds,etc.', and synthetic oils, like synthetic fatty'oil esters may also betreated. From the p0int.of view of this invention such above mentionedsynthetic resins and synthetic oils behave and count as fatty oils.

It is remarkable that even in such cases when the dissolution promotingagent partially evaporates or decomposes or forms some new chemicalcompound during the reaction of the heating process,' its originalbehavior in solvents seems to show up in the resulting fatty oilproduct.

With regard to proportions to be used 0.1% to 10% by weight, based onthe oil product, are the practical limits. Usually 2% to 5% produce verysatisfactory results.

The importance of this invention can be illustrated if a few practicalexamples are considered. Most thickened fatty oils, for instance, areinsoluble in acetone but if I incorporate in them dissolution promotingagents soluble in acetone, I obtain products which are acetone soluble'independently of their melting point or viscosity. (The melting pointand viscosity is, in the case of unmodified bodied oils, inverselyproportional to their solubility.) Further I have found that the hardera solidified linseed 011 product is, e. 8., the more quickly do thevarnishes, made of these oil products dry. The harder solidified oils,the melting points of which are higher, yield in the when used inconnection with most cases very viscous solutions in their solvents. Forcertain technical purposes it is important sometimes in the varnishtrade to have oil solutions with low viscosity. According to the presentinvention, if I incorporate a dissolution promoting agent, soluble inthe particular solvent or solvent mixture in question, I may obtaincomparatively mobile solutions even from hard modified oils. In theabove mentioned .processes, besides the primary modifying agents,

which are necessary to bring about any modification of the fatty oils,secondarily a dissolution promoting agent may be incorporated, whichitself does not modify the oil, but which influence the physicalproperties, and especially the solubility properties of the resultingproduct the primary modifying agent.

A further practical example is the incorporating of fatty oils intonitrocellulosesolutions for the manufacture of leathercloth or for themanufacture of lacquers.

In the manufacture of artificial leather or leathercloth fatty oils areused as softeners, acting' at the same time as an extender, ofnitrocotton, to reduce cost of the film to be produced. Thenitrocellulose is more expensive than the .fatty oils. Most oils howeverfiocculate the nitrocotton from its solution. This flocculation may bedue to incompatibility with they nitrocellulose, or as it is more oftenthe case, it is due to reduced solubility of the oil in thenitrocellulose solvents, or solvent mixtures, or, thinners. Only castoroil has been found as suitable for plasticizing nitrocellulose films inlarger proportions. Besides the fact that castor oil belongs to thehigher priced oils and other oils, like linseed oil, soyabean oil, fishoil, if could be made suitable, would be less expensive, the

castor oil has drawbacks which may also be improved. r

The drawbacks of castor oil are as follows:

.(1) It cannot be used in larger proportions than 2 to 1 part ofnitrocellulose. If more oil is used, the film gets tacky and loosesstrength. (2)

Castor oil sweats out (perspires) from leathercloth at elevatedtemperatures, e. g. near a fireplace or radiator, especially if it ispresent in substantial quantities in the film. Finally (3) castor oilshows bad ageing properties in leathercloth. All three drawbacks can beimproved if a modified castor oil is used. A heat bodied castor oil,especially the solid ones, do not sweat out of leathercloth or otherfilms and because of their hardness or high viscosity, have lessplasticizing effect than raw'castor oil has on nitrocellulose. Therebyfilms with dry appearance can be made with higher proportions than 2parts of oil to 1 part of nitrocellulose, parts being parts by weight.

Further according to the present invention it is possible to make asuitable plasticizer for nitrocellulose out of other less expensive anddomestic oils, such as linseed oil, soyabean oil, fish oils,amongst'others. Most modified linseed oil products, e. g. are insolublein solvents for nitrocellulose and flocculate therefore the A harder oilwith higher melting point has generally a less softening action oncellulose esters than raw castor. oil. Therefore if .such an oil is usedin a greater than 2:1 proportion with nitrocotton, the resulting filmwill show satisfactory properties, not having surface tack. Oil productswith higher melting point have naturally reduced perspiration tendencyif any. It is further possible, by choosing suitable dissolutionpromoting agents as modifying agents or in addition to such, to improvethe ageing properties of the leathercloth products. Dissolution.promoting agents, whichv when added in the proportion of 2% of theweight'of the oil to a solidified linseed oil, which has been solidifiedwith 5% NaHSO3,-will improve the ageing properties of the product, aree. g., alpha-naphthol, pyrogallol, p-aminophenol hydrochloride, benzoylchloride, cinnamic aldehyde, benzene sulphochloride, p-toluolsulphochloride, and also the inorganic thionyi chloride Nitrocelluloselacquers have many advantages over oil varnishes, but their mostimportant drawback is the cost of their production. The replacing ofsome of the nitrocellulose "with the less expensive fatty oil productsis a great advantage. A further problem with the nitrocellulose lacquersis that they have lower solids than varnishes. A clear furniture lacquerof high quality may have 24% to 30% solids in shipping consistency and15 to 20% solids at spraying consistency. A furniture varnish may beshipped with solids and in spraying consistency it may have 40 to 45%solids. For this reason the filling qualities of varnishes are betterthan those of the lacquers. With lacquers more coats are needed toproduce quality finishing than with varnishes. By the addition of themore or less heavily bodied fatty oil products to the lacquer,

ity properties in the lacquer solvent combination low temperatures), lowimproved properties. The a as applied. The high viscosity or solidity ofthe fatty oil permits the addition 'of larger proportions of oils to thenitrocotton, without, imparting too much softness to the film and causesimultaneously a deep looking effect, f. e. the film looks like aheavy-layer, in contrast to the looking single coat of a regularlacquer. As most oil products which are satisfactory in varnishes, willfiocculate the nitrocotton and are insoluble in lacquer solvents, theproblem is not simple.

According to the presentinventionhowever it is possible to produce awide range of modified oil products, which can easily be mixed withnitrocellulose and which yield satisfactory lacquers.

A further important feature of my invention is to prepare low viscositysolution of modified bodied oil products in varnish solvents, whichotherwise yield very highly viscous solutions in the same solvent,necessitating further dilution for brushing or spraying purposes. Suchsolidified oil products yield fast drying varnishes, but their regularsolutions are so viscous that when diluted to brushing consistency -orto spraying consistency their solids are again very much re--,

duced. By dispersing dissolution promoting agents in .such oils, (e. g.in an aftertreatment at viscosity solutions are produced with highersolids.

My invention is illustrated but not limited by the followinginebyweight.

tables and examples, the parts be- Phtlmlic annydrida s TABLE I Thesolubility of modifying and/or dissolution promoting agents in certainorganic solvents Solvents Type of reagent Methyl ol- Butyl ace- Acctonecon 01 Bcnzol mm 4 Inorganic modifying and simultaneously dissolutionpfo-mol- 511a agents Sodium iodide S Sodium bromide" Ammonium lOdidGCalcium oxalate- Magnesium chloride.

Zinc bromide S Potassium sulfldc Sodium tbiosul[atc.

Aluminum carbonate. Strontium sulfide Oraanic modifying andsimultaneously dwrolulio'n. promoting agents, [1081C Urea Meta-xylldmeAc dic, or containing acidic residues Benzoic acid w re? Amido-G-saltBcta-oxynaphtoi acd. Meta-xylidme sulio acid Dimethyl suliatc Monochloracetic acid. 2:6 naphtalin disulio old Tobias acid Dichlorbenzenc.luoresceinc...

o-Nitrophenol.

Dlnitraniline.

2:5 dichlorbene sulio acid. Triphenyl hosphate. S. p-Aminop enol by- Idrochloride. p-Toluidine m-sulio acid. p-Toluol sulio chloride.o-Dlchlorbenzol p-Nitro acctamhde- Do p-Chlot o-anisldme p'NltropbenolNonmodifuing organic dissolution promoli'nu agents Alpha-us htol G ucosePhenol (CBrbOllC acid).

Resorcinol p-Cresol o-Gresol I i" F 7 2 00mg g 4012mm O O S, soluble; om the cold; I, insoluble; 81. S, slightly soluble; -V,

very; M, mis

Example 4.-100 parts of castor oil are heated together with 5 partsammonium iodide in vacuo of 100 mm./Hg pressure for 5 hours at 260 C. Adark colored soft paste is obtained which is soluble in acetone.Ammonium iodide is soluble in acetone. Ammonium iodide causes goodsolubility in many lacquer solvents, whereas replac-' ing ammoniumiodide with the acetone insoluble lithium carbonate as modifying agent,the resulting product has'no solubility in acetone.

Example 5.-100 parts or castor oil modified by five parts of bariumthiocyanate under the conditions of Example 1, yields a brown mobile oilwhich is soluble in butyl acetate and benzol.

*of mm./Hg pressure.

also soluble in these solvents.

Barium thiocyanate is soluble in butyl acetate and is moderately solublein benzene. Increased temperature and duration of heating increases theviscosity of the 011 product. In case of more viscous oils prepared withthe same modifying and dissolution promoting agent, the solubility issomewhat reduced, but the action of the dissolution promoting-agents isstill pronounced Example 6.--100 parts of castor oil is treated with 5parts of cadmium iodide as described in Example 1. (A viscous oil isobtained which is acetone soluble, as is cadmium iodide itself.)

Example 7.-100 parts of castor oil are treated with 5 parts of zincbromide at 250 C. in vacuum After the heating proceeded properly the oilgels in vacuum. Therefore it is advisable to reduce the amount of zincbromide to 2 parts, to heat to 200 C., to hold there for 2 hours, heatin further 20 minutes to 230 C. and to hold there for 3 hours. Theproduct is a viscous brown oil, soluble in acetone as well as in butylacetate. \The reagent itself is If the reaction is repeated in opencontainers under atmospheric pressure, the product is thicker and is inthe cold an elastic solid. It has still good solubility properties inthe solvents in which zinc bromide is soluble.

Example 8.-100 parts of castor oil, 2 parts of lithium carbonate and 5parts of beta-naphthol are treated in the manner described in Example 1.Temperature of 200 C. is reached in 20 minutes. This temperature is heldtor 3 hours, the temperature raised to 250 C. and held for 6 hours. Theproduct is a soft pasty light. brown solid, having good solubilityproperties in lacquer solvents. If in this example castor oil isreplaced by linseed oil, and the temperature raised in the last 6 hoursto 290 to 300 0., a more solid product is obtained, with satisfactorysolubility properties. Soyabean oil yields softer products and fish oilpasty products of medium consistency.

Example 9.-100 parts of castor oil is treated with 5 parts of2:5-dichloro-benzenesulfonic acid, as described in Example 1. Theproduct is a thick viscous oil, soluble in butyl acetate, acetone andbenzene. The reagent itself is also soluble in those solvents. Ifinstead of 2:5-dichlorobenzenesulfonic acid other dissolution promotingmodifying agents are used, the following results are obtained: benzidinebase yields a semisolid, p-nitrochlorbenzene .a thin brown oil,dichlorbenzene yields a mobile light oil. If p-cresol is used asnonmodifying dissolution promoting agent alone, a clear viscous oil isobtained with similar consistency, than castor oil when heated undersimilar conditions. All products have good solubilities in the abovethree solvents and also in other lacquer solvent mixtures.

Example 10.--When 100 parts of linseed oil is treated with 3 parts ofcalcium peroxide and 3 parts of zinc sulphite at 290 to 300 C. in theway as described in Example 1, a tough solid results upon cooling, whichmay be used as varnish base, e. g. with lime hardened rosin as resinconstituent. If varnishes with the usual no volatile content areprepared with this material very viscous solutions result, which oughtto be further diluted to be useful for brushing or spraying purposes.Very dilute solutions with low solid content are'not liked by users, asthe resulting films are very thin and a considerable number of coatswould have to be applied to obtain satisfactory coating thickness. If e.g. 4 parts of p-nitrophenol or 4 parts of benzoic acidare dispersed inthe above linseed oil product by the aid of heat, heating the mixtureonly, to th point when it yields a homogeneous mass, on cooling aproduct is obtained which yields in turpentine much less viscoussolutions than the original product. 5 ;taining p-cresol as dissolutionpromoting agent P-nitrophenol, o-nitrophenol and benzoic acid aloneyield also satisfactory results. As the are soluble in turpentine.alcohols are usually bad solvents for bodied Instead of castor oil orlinseed oil in the above oils, coaltar hydrocarbons may be wellexamples, other oils or resins may be treated in used as thinners. Ifduring preparation the a similar way. Examples for such oils are: tung lnitrocellulose precipitates, addition of ester type oil, soyabean oil,fish oils, sunflower oil, perilla oil, solvents, such as amyl acetate,butyl acetate, ethyl oiticica oil, etc. Examples for the resins areacetate may correctthe trouble. The higher alkyd resins containing fattyacids or fatty oils boiling esters are usually better solvents for oils.as resin ingredients. The resins are usually more Other mutual solventsmay also be used. P-toluol readily soluble in nitrocellulose solvents,than oils. l sulfonic acid yields also satisfactory properties.

Example 11.-To manufacture a dope suitable Example 12.100 parts ofnitrocellulose, for leathercloth manufacturing 20 parts of a parts oftricresyl phosphate, 100 parts of castor nitrocellulose solution inacetone or ethyl acetate oil product of Example 6, containing 2:5dichloris used. To this quantity of solution 10 parts of benzol sulfonicacid, 100 parts of rosin-glycerineoil product isadded. The oilshouldbegradually 2o ester (ester gum) and 100 parts of a long oilstirred into the nitrocotton solution. If the oil castor oil alkyd resinare dissolved in a 40 to is too heavy, it may be dissolved in a part ofthe amyl acetate and-50 to coal tar hydrocarbon diluent. Thenitrocellulose is usually a 5 to 10 (such as toluol or xylol) containingsolvent mixseconds quality. About 50 parts by volume of ture to a totalsolids of 20 to 25%. The resulting diluent is needed to parts by volumeof the lacquer is a satisfactory wood lacquer, having combinedoil-nitrocellulose mixture. As diluent good filling qualities, but notsuitable to rubbing. isopropyl or ethyl alcohol may be used, contain-Many of the above examples yield satisfactory ing 10% of amyl acetate.The latter is a good compatibility in chlorinated rubber varnishes,mutual solvent of oil and nitrocellulose and seethyl cellulose lacquer,etc. Good solubility may cures uniform drying. The diluent should be 30also be obtained in tetra chlor ethane and similar added gradually.Modified castor oil products with good solubility properties in lacquersolvents may be used, such as the ones treated with ammonium iodide,ammonium chloride, benzidine List of experiments ionic acid, bariumthiocyanate plus p-cresol. p-nitrophenol. A heatbodied castor oil,consolvents. Methyl ethylketone, butyl alcohol, isopropyl alcohol,glycol ethers are amongst the other important solvents, in which goodsolubility may be obtained.

TABLE II to modify castor oil and to influence solubility of bodied oils[This is an incomplete but demonstrative list] Inorganic modifyingagents Soluble in organic solalone vents Plus organic dissolution pro- IInsoluble in organic moflng agents solvents alone Barium thiocyanate.HgCh- LiiOO; plus pcresol LigSO plus p-cresol LizSOi plus phenol LlzCOsplus phenol LEGO! plus alpha-naphthol LlzCOa plus beta-nziphthol LnSOaplus beta-naphthol LizSO; plus alpha-naphthol base, lithium sulfite pluscarbolic acid In carbonate plus D-cresol, 2:5-dichlorobenzene sul-Organio modifying agents, soluble in organic.

, so vents 2:5 dlchlorobenzol-sulionic acid o-Nitrophenol g Nitrophenolnzidine bus p-Nitro ohlorbenzene p-Nitro phenol, and p-cresoi o-Cresolp-Toluol sulionic acid p-Toluol sulfon chloride Aoetyl chloride Benzoyichloride of inorganic and organic agents, both lub e in organic solventsBarium thiocyanate ins p-crs 01 Barium thiocyanate glue phenol x Themodified castor oil products have also useful drying properties and maybe used in preparation of varnishes. If only drying isimportant, thensmaller proportions of reagents may be added, such as fractions of 1%,like 0.1%, or 0.2%,0.05%.

The modifying agents herein described are polar compounds. .Polarcompounds contain a positive charge in one part of the molecule and anegative charge in another part of the mole-- cule. A polar compoundwhich is soluble in an organic solvent, is a dissolution-promoting polarcompound or one which has dispersing properties.

What I claim is:

1. A coating composition, comprising a solution of a cellulosederivative lacquer base chosen from the class consisting of celluloseesters and ethers in an organic solvent, and also comprising a fatty oilhaving dispersed therein at Ya temperature of 100 C. to 300 C. not morethan percentof a polar compound but enough to improve dispersingproperties in said solution, said polar compound having dispersingproperties due to its being soluble in said solvent, the ratio of saidfatty oil to said lacquer base being greater than unity and saidsolution being free from tendency to fiocculate.

2. The composition of claim 1, in which the lacquer base is a celluloseester.

3. The composition of claim 1, in which the lacquer 'base, isnitrocellulose.

4. The composition of claim 1, in which the polar compound is a solidorganic polar compound that is soluble in organic solvents.

5. The composition of claim 1, in which the polar compound is a solidorganic polar compound that is soluble in organic solvents containing anacidic inorganic residue and an organic residue in the molecule.

6. The composition of claim 1, in which the polar compound is a solidorganic polar com-- pound that is soluble in organic solvents containingan aromatic residue and a hydroxy group in the molecule.

:- 7.The composition of claim 1, in which the polar compound is a solidorganic polar compound that is soluble in organic solvents, said polarcompound containing an amino group in the molecule.

8. The composition of claim 1, in which the 'fatty oil is a non-dryingoil.

9. The composition of claim 1, in which the fatty oil is a drying oil.

10. The composition of claim 1, in which fatty oil is linseed oil.

11. The composition of claim 1, in which the fatty oil is castor oil.

12. The process of producing a coating composition that is free fromtendency to flocculate, which comprises dissolving in an organic solventa cellulose derivative lacquer base chosen from the class consisting ofcellulose esters and ethers and adding a fatty oil having dispersedtherein at a temperature of C. to 300 C. not more than 10 percent of a'polar compound but enough to improve dispersing properties in saidsolution, said polar compound having dispersing properties and beingsoluble in said solvent, the ratio of said fatty oil to said lacquerbase being greater than unity. Q

13. The process of claim 12, in which the lacquer base is a celluloseester.

14. The process of claim 12, in which the lacquer base isnitrocellulose.

15. The process of claim 12, in which the fatty oil is a non-drying oil.

16. The process of claim 12, in which the fatty oil is a drying oil.

1'7. The process of claim 12, in which the fatty oil is linseed oil.

18. The process of claim 12, in which the fatty oil is castor oil.

the

LASZLO AUER.

Certificate of Correction August s, 1942.-

Patent No. 2,293,038.

v LASZLO AUER v I It is hereby certified that errors appear in theFrinted specification of the above, numbered patent requiring correctionas follows: age 3, first column, line 21, for Pipe oil read Pine oil; pae 4, second column, line 67, for Mono-btuyl read Mono-butyl; p e 8,first co umn, line 10, for the words .of on read or on;page 10,

first column of able I, lines 21 to 29 in'clusive,'for

"Of Me mod 01 Mile medi yin or? minimum a ed dumbed: diuolutton mmumampromot- M mm. c Mm:

Ema-mam v Benzidhebase...-.- read 'etw iidine.......

Acflfi or containing base..-"

WW a? smear;

Benzoic sold I Y n.aa1t.---..'.'.IIIIII page 11, Table H,in the heading,for Y I Inorganic modiiying agents mm ma g msaohgion BolnbieinorganieInsolublein solvents alone solvents 111 read Inorganic modifying amt!Insoluble in organic solvents Soluble; in caganic so van 7 Plus organicdissolution V 0 romoting agents and that the said Letters Patent shouldbe read with these" corrections therein that the sa ne may conform tothe record of the casein the Patent Oflice.

Signed and sealed this 12th day of January, A; D.- 1943.-

[SEAL] HENRY VAN TARSDALE,

Actiizg Commissioner of Patents,

i Patent No.2,293,038.

Certificate of Correction v f August18,1942. v LASZLOAUER It is herebycertified that errors appear in the rinted s ecification of the abovenum patent requiring correction as follows: age 3, t column; line 21,for Pipe oilread-Pine all; p e4, second column, line 67,-for Mono-btuylread M -.W; P 8 first co umn,hne 10, for the words .ofou read oron;'page 1.0, first column of abie I, lines 2 1 to 29 inclusi'v qf'or vMia:- 0 m 04min:

n mmm fi'r uamxz: read Um A or lcrqdduu linoleum 11.1m

- [sun] lnoiiinlem d fflnlmts 1 801 mum! Ineol bleinerau .am PM... readI lncqmicmodlmngl entl lnlolublelnmieiolventu Soluflginznuie t Plumbdheomtlon end that the Letters Patent should be read with thesecorrections therein that the se ne may conform to the record of thecasein the Patent Ofiice. Signed and sealed this 12th day of January, A.D.- -1943.-

HENRY VAN ARSDALE,

Commissioner of Pctents r

